Cleaning composition with improved bleaching effect

ABSTRACT

CLEANING-COMPOSITION WITH IMPROVED BLEACHING EFFECT AT MODERATE TEMPERATURES SUCH AS ABOUT 20*-60*C. COMPOSITION CONTAINS MINERAL, PERSALT, ORGANIC ACTIVATOR THEREFOR, CUPRIC SALT AND COPPER COMPLEXING AGENT.

3,583,924 Patented June 8, 1971 United States Patent Office ABSTRACT OF THE DISCLOSURE Cleaning composition with improved bleaching effect at moderate temperatures such as about 2060 C. Composition contains mineral, persalt, organic activator therefor, cupric salt and copper complexing agent.

The present invention relates to compositions for cleaning linen, dishes and other household articles.

By the expression cleaning compositions are understood as well compositions destined to exercise essentially a bleaching efiect on treated materials as well as those destined to exercise, besides this eifect, an effect of detergency, such as the washing and scouring compositions.

It is an object of this invention to provide a composi tion, which, whatever may be its destination, exercises an improved bleaching effect and this, in a domain of moderate temperatures, typically about 20 to 60 C. Other objects will be apparent from consideration of the following description.

In accordance with certain of its aspects, this invention relates to a cleaning composition comprising a mineral persalt, an organic activator therefor, a water soluble cupric salt and a copper complexing agent.

Cleaning compositions have been prepared containing a mineral persalt, as a bleaching agent, and an organic activator in order to lower the zone of temperatures where the bleaching effect is the best.

Furthermore, unactivated bleaching compositions containing a persalt and effective at the boil have been prepared which contain:

A quantity of cupric salt such as that the content in copper of the bleaching solution, utilized at low temperature may be from 0.5 to 10 parts per million (ppm); (French Pat. 1,183,646);

A cupric salt and a complexing agent forming a metal buffer maintaining the content in copper ions of the bleaching composition utilized under boiling at a relatively constant value (US. Pat. 3,211,658).

According to the invention it has been discovered that the quadruple association-persalt, activator, cupric salt and complexing agentyield as far as their bleaching effect at moderate temperatures is concerned, higher results than those which could have been expected from the state of the art.

Moreover, the best results are obtained in the instant invention when the contents of copper are distinctly higher than that previously recommended and the proportions of copper to complexing agent clearly different from previous proportions.

The mineral persalt is advantageously a perborate and especially a sodium perborate by reason of the ease of obtainment and the cost of these compounds. However, other persalts may be used.

The activator for the persalt can be:

Phenol acids such as acetyl salicylic acid and phenol esters such as described in French Pat. 1,155,228 including phenyl acetate, phenyl benzoate, phenyl p-nitrobenzoate, phenyl cinnamate, cresyl acetate, o-nitrophenyl benzoate, o-carboxy phenyl benzoate, o-carboxyphenyl acetate, p

carboxy phenyl acetate, p-phenyl acetate, phenyl furoate, p-bromophenyl benzoate, salicyl acetate and p-sulfophenyl benzoate of potassium or sodium, and of French Pat. 1,338,579 such as chloroacetoxy benzene, p-chloroacetoxy benzene sulfonate of potassium, m-chloroacetoxy benzene carboxylic acid, m, p-trichloroacetoxy benzene carboxylic acid, o-chloroacetoxy benzene carboxylic acid, and oalphachloropropionoxy benzene carboxylic acid;

The anhydrides of acids of French Pat. 1,154,344 such as benzoic anhydride and propionic anhydride;

The acylamides and acylamines of French Pat. 1,232,554 such as N,N-diacetyl-p-toluidine, N,N-diacetyl-p-chloroaniline, N,N-dibutyryl aniline, dibenzanilide, N-acetyl caprolactam, N,-N'-diacety1 barbitone, N-acetyl phthalimide and N-acetyl saccharine and of French Pat. 1,258,- 675 such as diacetyl ethyl amine, diacetyl propylamine, diacetyl butylamine, diacetyl benzylamine, diacetylaniline, diacetamide, dipropionamine, N-formyl diacetamide, N- acetyl diacetamide, triacetamide, N-propionyl diacetamide, N-butyryl diacetamide, N-valeryl diacetamide, N-caproyl diacetamide, N-acetyl phthalimide, N-acetyl succinimide, N,N-diacetyl cyanamide, N,N-diacetyl ethyl urethane, N- acetyl-N-propionyl ethyl urethane, triacetyl hydrazine, tetra-acetyl hydrazine, tripropionyl hydrazine, N,-N-diacetyl N'-benzoylhydrazine, -N,N-diacetyl-N'-isopropyl idene hydrazine, triacetyl methylene diamine, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, tetraacetyl hexamethylene diamine, tetra-acetyl phenylene diamine, and N-diacyl semicarbazides, thiosemicarbazides, and dicyanodiarnides.

The acylamides of French Pat. 1,315,745, such as diacetyl hydantoin, 5,5-dimethyl monoacetyl hydantoin, 5,5- dimethyl diacetyl hydantoin, 5,5-dimethyl monopropionyl hydantoin, 5,5-dimethyl benzoyl hydantoin, and of U8. Pat. 3,061,550, such as N-benzoyl succinimide, N-p-anisoyl succinimide, N alpha naphthoylsuccinimide, N-betanapthoylsuccinimide, N-benzoyl glutarimide, N-p-chlorobenzoyl succinimide, N,N-dibenzoylformamide, N,N-dibenzoyl acetamide, 1,3-dibenzoyl dimethylhydantoin, N- benzoylphthalimide, N-benzoyl-pyrrolidone, N-cinnamoylsuccinimide and N-m-nitrobenzoyl succinimide; and

Triacetyl cyanurate.

Although it is difficult to define in a general way the different activators, they can be considered as answering to the formula:

in which:

Z is an aryloxy, acylamido, acylimido, acyloxy radical or a radical derived from carbonic acid such as the ureido and guanidino radicals, which may be substituted or unsubstituted and,

R is a substituted or unsubstituted aliphatic, non-aromatic cyclic or aromatic radical.

Any water-soluble cupric salt is utilized according to the invention, appropriate examples being cupric sulfate, chloride, acetate, nitrate and bromide.

Examples of copper complexing agents include the organic complexing agents ethylene diamine tetracetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), methylimino diacetic acid, aminotriacetic acid, hydroxyl ethylimino diacetic acid and their water-soluble salts.

The content in persalt of the composition depends on the use for which it is destined.

As for the constituents of the composition which particularly affect the bleaching, their contents are advantageously controlled in the following way, in order to v obtain the best results.

The content in activator is such so that the molecular ratio of the activator to persalt is between about 1:5 and :1 preferably between about 1:2 and 2:1.

The content in cupric salt is such that the amount of copper ions or atoms dissolved when the composition is used, is between about 2 and 100 p.p.m., preferably about 5 and 60 p.p.m. parts of solution.

Considering the fact that the composition is generally utilized on the average, at the rate of about 5 g./l., its content in copper is therefore advantageously from about 400 to 20,000 p.p.m., preferably from about 1000 to 10,000 p.p.m. parts of cleaning composition.

The contents in complexing agent is such that for each atom of copper the composition contains about 0.02 to molecules, preferably 0.4 to 2, of complexing agent.

The complete formulation of the composition according to the invention varies according to the usage to which it is destined. If only a simple bleaching effect is required the composition will be a simple mixture of a persalt, an activator, a complexing agent and a copper salt. However it is possible to add to the composition secondary components such as minerals, perfumes, optical agents, etc. Compositions of this type can be then used alone or mixed with surface active agents in washing or cleansing products.

More complex compositions destined as indicated for a more complete action than the bleaching alone, likewise enter into the scope of the invention.

To this category belong compositions destined for washing linen containing in addition to the persalt, activator, the complexing agent and the cupric salt, one or several synthetic detergents such as alkyl benzene sulfonates, ethoxylated alkyl phenols, sulfated or not, ethoxylated fatty alcohols, sulfated or not, ethoxylated fatty acids, condensates of ethylene oxide and of propylene oxide (eventually soap), various mineral salts which do or do not have an adjuvant action of detergency (phosphates, silicates, sulfates, alkali metal carbonates), products preventing the redeposition of soil on the linen, optical bluing products, anticorrosion products, etc. These compositions are destined in principle for washing linen at moderate temperature, but they can be also used for washing at the boil, while taking advantage of their bleaching effect at this temperature of the washing bath. Closely related compositions which may be prepared are scouring compositions containing, in addition, an abrasive such as silica.

These compositions can be manufactured according to all known processes starting from the simple mixture of powders in spray drying of a simple aqueous slurry. Care Percent Detergent (synthetic detergent soap or their mixtures) Mineral Salts having or not having an adjuvant action on detergency 40 to 90 Perfume, colorant, bluing agent 0 to 1 The following examples illustrate the invention with however limiting the same in these examples. The contents in various constituents are given in parts by weight,, except contrary indications.

4 EXAMPLE I Composition for washing linen in machines at moderate temperature, utilizable at 5 g./l.

Percent Sodium dodecylbenzene sulfonate 8 Nonyl phenol of 9.5 molecules of ethylene oxide 3 Tallow Soap n V 8 Sodium tripolyphosphate 3.5 Sodium silicate 8 Sodium perborate 8 Tetra-acetyl methylene diamine 5.5 Sodium salt of amino triacetic acid 0.4

CUSO4.5H2O

Sodium sulfate, moisture and various products (perfume, colorant, bluing agent, solid antiredeposition agent) q.s. to 100.

EXAMPLE II Composition for hand washing linen at moderate temperature, utilizable at 8 g./l.

Percent Sodium tridecyl benzene sulfonate Sodium tripolyphosphate Sodium silicate 6 Sodium perborate 6 Triacetyl cyanurate 5 CUSO4-5H2O Various products, sodium sulfate, moisture q.s. for 100.

EXAMPLLE III Controlled foam composition, utilizable for hand or machine washing, utiliza'ble at 5 g./l.

Percent Sodium tetrapropylene benzene sulfonate 10 Tallow soap z 10 Sodium tripolyphosphate Sodium silicate 8 Magnesium sulfate 1 Sodium perborate 8 Tetra-acetyl methylene diamine 5.5 Sodium salt of aminotriacetic acid 0.4 CuOAc.H O 0.6

Various products, sodium sulphate moisture q.s. for 100.

EXAMPLE IV Foaming composition for washing in lixiviating apparatus, utilizable at 5 g./l.

Percent Sodium dodecyl benzene sulfonate 12 Sodium salt of sulfated fatty alcohol 6 Fatty acid ethanolamide 2.5 Sodium tripolyphosphate 30 Sodium carbonate 10 Magnesium silicate 1 Sodium perborate 8 Triacetyl cyanurate 5 Sodium salt of aminotriacetic acid 0.4 CuSO .5H O 0.8 Various products, sodium sulfate moisture q.s. for 100.

EXAMPLE V Bleaching composition for use of 2 g./l.

Percent Sodium tripolyphosphate 20 Sodium perborate Tetracetyl methylene diamine 30 Sodium salt of ethylene diamine tetracetic acid 1 CuSO .5H O 2 Various products, sodium sulfate moisture q.s. for 100.

The following tests evidence the improved bleaching effect obtained according to the invention. The following washing composition (A) is prepared:

Sodium tridecylbenzene sulfonate 30 Sodium tripolyphosphate 35 Sodium silicate 8 Sodium perborate 13.5

Various products, sodium sulfate, moisture, q.s. for

To 75 parts by weight of this composition (A) are added 25 parts by weight of following additives, carefully ground and homogenized:

'Iriacetyl cyanurate Acetylsalicylic acid". Para-acetoxybenzene sulfonate of sodium .2 Sodium sulfate 62 62 Quantity suflicient for 100 The mixtures of composition (A) with additives No. 1 to 9 result in corresponding compositions A A A A4, A9.

The bleaching efficiency (EB) of these compositions has been determined in the following Way:

Samples of cotton fabric are dyed by means of a colorant pyrogene black (Ciba) and washed in absence of oxidizing agent until complete elimination of excess of colorant. These dyed fabrics, whose reflectance is of the order of 20, are washed with the above compositions A to A at 5 g./l. for /2 hour at 40 C. and 60 C. The bleaching efficacy of compositions is expressed by the relation Rg-R The following are the obtained results:

E. B. at

After 1 After 3 After 1 After 3 Composition wash washings wash washings These results clearly show that the compositions of the invention (A, to A are highly superior over the activated compositions (A to A which containneither cop- Composition: EB. percent A 4.8 A 5.0 A 2.6 AC, 4.6

These results are clearly inferior than that obtained with compositions A to A and even than the ones obtained with compositions A to A In the same way, if in compositions A to A, the complexing agent is removed so that persalt, activator and copper are present, the following results are obtained.

Composition: E.B. percent A" 8.2 ug 1 A 2.4 A"., 3.2

There also, the results are very clearly lower than the ones obtained with compositions A to A as well as lower than those obtained with compositions A to A and about equal to A From the preceding it is clear that highly improved bleaching is effected by the simultaneous presence of a mineral persalt, of an activator of this persalt, of a cupric salt and of a complexing agent.

Naturally, the invention is not limited to the described methods of working which have been only given as examples.

We claim:

1. A cleaning composition effective at about 20 to 60 C. consisting essentially of about 1-80% by weight of a sodium perborate; an organic activator therefor having the formula:

in which Z is a substituted or unsubstituted radical selected from the group consisting of aryloxy, acylamino, acylimido, acyloxy, ureido and guanidino and R is selected from the group consisting of alkyl, substituted phenyl and unsubstituted phenyl, the ratio of said activator to said perborate being between 1:5 and 5:1; a water-soluble cupr1c salt in an amount which provides between about 400-20,000 p.p.m. of copper atoms in said composition, and an organic copper complexing agent selected from the group consisting of ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, methylamino diacetic acld, amino tetraacetic acid, hydroxyl ethylimino diacetic acid and water-soluble salts thereof, there being present about 0.02 to 10 molecules of complexing agent for each gram atom of copper present.

' 2. The cleaning composition claimed in claim 1 where- 1n said sodium perborate is present between about 20% and 3. The cleaning composition claimed in claim 1 wherein said sodium perborate is present between about 3% and 15%.

4. The cleaning composition claimed in claim 1 wherein said molecular ratio of said organic activator to said sodium perborate is between about 1:2 and 2:1.

5. The cleaning composition claimed in claim 1 wherein said organic activator is selected from the group consisting of tetraacetyl methylene diamine, triacetyl cyanurate, acetylsalicylic acid and p-acetoxybenzlene sulfonate.

6. The cleaning composition claimed in claim 1 wherein said water-soluble cupric salt is selected from the group consisting of cupric sulfate, cupric chloride, cupric acetate, cupric nitrate and cupric bromide.

7. The cleaning composition claimed in claim 1 Wherein said water-soluble cupric salt is present in amount sufficient to provide a copper atom concentration of between about 1,000 and 10,000 p.p.m. and said copper complexing agent is present in amount such that about 0.4 to 2 molecules thereof are present for each atom of copper.

8. The cleaning composition claimed in claim 5 Wherein said organic activator is tetraacetyl methylene diamine.

9. The cleaning composition claimed in claim 5 wherein said organic activator is triacetyl cyanurate.

10. The cleaning composition claimed in claim 6 wherein said water-soluble cupric salt is CuSO -5H O.

11. A cleaning composition effective at about 20 to 60 C. consisting essentially of about 1% to 80% by weight of sodium perborate; an organic activator therefor selected from the group consisting of tetraacetyl methylene diamine, triacetyl cyanurate, acetylsalicylic acid and p-acetoxybenzene sulfonate; the ratio of said organic activator to said sodium perborate being about 1:5 to 5:1 by weight; a water-soluble copper salt selected from the group consisting of cupric sulfate, cupric chloride, cupric acetate, cupric nitrate and cupric bromide in amount sufficient to provide a copper atom concentration of between about 400 and 20,000 parts of copper atoms per million parts of said cleaning composition; and a copper complexing agent selected from the group consisting of ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, methylirnino diacetic acid, aminotriacetic acid, hydroxyethylimino diacetic acid and water soluble salts thereof; said copper complexing agent being in amount such that about 0.02 to 10 molecules thereof are present in said cleaning composition for each atom of copper.

References Cited UNITED STATES PATENTS 2,955,905 10/1960 Davies et a] 25Z103 3,130,165 4/1964 Brocklehurst 252--99 3,163,606 12/1964 Viveen et al. 252-98 3,177,148 4/1965 Bright et al 25299 3,211,658 10/1965 Hirtz et a1 25299 3,349,035 10/1967 Dithmar et al 252--99 3,425,786 2/1969 Dithmar et al 252-99X MAYER WEINBLATT, Primary Examiner U.S. Cl. X.R. 252-95, 99, 186 

